LAUSR

Tri‐ and tetrasubstituted alkene scaffolds are prominent building blocks in many bioactive natural products, drug molecules, and key intermediates in various synthetic transformations. The dual functionalization of alkynes promises an easy introduction of functional groups across the triple bond with a high step and atom economy, exemplifying a class of reactions to construct tri‐ and tetrasubstituted alkene scaffolds. This review discusses the versatility and advances in the transition metal‐catalyzed redox dual functionalization of alkynes, their unique mechanistic features, and the synthetic applications of the methodology. This collection focuses on the formation of simultaneous C−C/C−X bonds involving various oxidation states of the metals in the catalytic cycle. Apart from the classical redox reactivity, radical‐mediated functionalizations are also discussed in detail.